CN114931863B - Conductive forward osmosis membrane and preparation method and application thereof - Google Patents
Conductive forward osmosis membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN114931863B CN114931863B CN202210539765.7A CN202210539765A CN114931863B CN 114931863 B CN114931863 B CN 114931863B CN 202210539765 A CN202210539765 A CN 202210539765A CN 114931863 B CN114931863 B CN 114931863B
- Authority
- CN
- China
- Prior art keywords
- membrane
- forward osmosis
- osmosis membrane
- solution
- polydopamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 153
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001690 polydopamine Polymers 0.000 claims abstract description 53
- 239000002105 nanoparticle Substances 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003245 coal Substances 0.000 claims abstract description 23
- 239000004952 Polyamide Substances 0.000 claims abstract description 17
- 229920002647 polyamide Polymers 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 71
- 239000010410 layer Substances 0.000 claims description 20
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 19
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 11
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 11
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000003828 vacuum filtration Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 9
- 238000000691 measurement method Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
- 238000009285 membrane fouling Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 230000035699 permeability Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- AMMWFYKTZVIRFN-UHFFFAOYSA-N sodium 3-hydroxy-4-[(1-hydroxynaphthalen-2-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S(O)(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of water treatment membranes, and discloses a conductive forward osmosis membrane, a preparation method and application thereof, wherein a tubular coal-based carbon membrane is used as a supporting layer, polydopamine nano particles are deposited on the inner surface of the tubular coal-based carbon membrane by a vacuum filtration method, and then a continuous polyamide layer is prepared on the surface of the polydopamine nano particles by interfacial polymerization to obtain the conductive forward osmosis membrane; the electrically conductive forward osmosis membrane can be used in water treatment, for example as a filtration membrane in a water treatment device or apparatus. The conductive forward osmosis membrane prepared by the method realizes good conductivity and chemical stability, and can solve the problems of poor conductivity or unstable conductivity of the composite conductive forward osmosis membrane; the method is applied to the field of sewage treatment, and can relieve the pollution of the forward osmosis membrane by combining the electrochemical action, so that the performance of the membrane is improved, and the method has great theoretical significance and application value.
Description
Technical Field
The invention belongs to the technical field of water treatment films, and particularly relates to a conductive forward osmosis film, a preparation method and application thereof.
Background
The forward osmosis technology is considered as one of the best strategies for relieving the problem of water resource shortage due to the advantages of low energy consumption, good effluent quality and the like. At present, forward osmosis technology is widely applied in the fields of sea water desalination, wastewater treatment and the like. However, membrane fouling prevents the forward osmosis technology from maintaining performance in long term applications. Thus, mitigation of membrane fouling is one of the main ways to improve membrane performance. The electrochemical coupling film technology is receiving more and more attention in the aspect of controlling film pollution because of the good characteristics of easy process control, stable performance, environmental friendliness and the like.
The conductive forward osmosis membrane and the electrochemical coupling have remarkable effect on relieving membrane pollution under the action of static electricity and oxidation. It has been proposed to enhance the membrane properties by introducing conductive materials on the surface of the forward osmosis substrate or polyamide layer, but conductivity or conductivity stability affects the enhancement of the membrane properties.
Disclosure of Invention
The invention aims to widen the preparation method of a conductive forward osmosis membrane, and provides a conductive forward osmosis membrane, a preparation method and application thereof, wherein a tubular coal-based carbon membrane with conductive performance is used as a supporting layer, polydopamine nanoparticle dispersion liquid is firstly subjected to suction filtration to the inner surface of the coal-based carbon membrane, then a polyamide layer is obtained through interfacial polymerization, and the prepared conductive forward osmosis membrane has good conductivity and stability, and can effectively relieve organic pollution of the forward osmosis membrane in the sewage treatment process by combining an electrochemical technology.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, a preparation method of a conductive forward osmosis membrane is provided, wherein a tubular coal-based carbon membrane is used as a supporting layer, polydopamine nano particles are deposited on the inner surface of the tubular coal-based carbon membrane by a vacuum filtration method, and then a continuous polyamide layer is prepared on the surface of the polydopamine nano particles by interfacial polymerization, so that the conductive forward osmosis membrane is obtained.
Further, the method comprises the following steps:
(1) Preparing polydopamine nanoparticle dispersion liquid;
(2) Preparing a polydopamine nanoparticle interlayer: allowing the polydopamine nanoparticle dispersion liquid obtained in the step (1) to pass through the tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum suction filtration;
(3) And preparing a continuous polyamide layer on the surface of the polydopamine nanometer particle through interfacial polymerization.
Further, in the step (1), the preparation method of the polydopamine nanoparticle dispersion liquid comprises the following steps: mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; oscillating the dopamine hydrochloride solution for 0.5-1.5 h to oxidize and self-polymerize the dopamine hydrochloride to obtain a polydopamine solution; and performing ultrasonic dispersion on the polydopamine solution to obtain the polydopamine nanoparticle dispersion liquid.
Wherein preferably, the dopamine hydrochloride powder is used in an amount of 0.1-0.2 g based on 100mL of water; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
Further, in the step (2), the deposition amount of the polydopamine nanoparticles on the inner surface of the tubular coal-based carbon film is 0.4-1.3mg/cm 2 。
Further, in the step (3), the method for preparing the continuous polyamide layer on the surface of the polydopamine nanoparticle by interfacial polymerization comprises the following steps: vertically fixing the membrane obtained in the step (2), enabling 1-7% of m-phenylenediamine solution to pass through the inner surface of the membrane at a flow rate of 1-5 mL/min, soaking for 1-10 min, and removing superfluous solution on the surface; then enabling 0.1 to 0.3 mass percent of trimesic chloride solution to pass through the inner surface of the membrane to react for 1 to 5 minutes at the same flow rate; after standing for a certain time, placing the membrane in a hot water bath for crosslinking; then taking out the membrane and sequentially placing the membrane into sodium hypochlorite solution and sodium bisulphite solution for soaking; and then placing the membrane in a hot water bath again to obtain the conductive forward osmosis membrane.
Wherein preferably, the resting time is 3-5 min; the temperature of the cross-linking in the hot water bath is 80-100 ℃ and the time is 1-3 min.
Wherein preferably, the concentration of the sodium hypochlorite solution is 0.1-0.5 g/L, and the soaking time is 1-3 min; the concentration of the sodium bisulfite solution is 1-3 g/L, and the soaking time is 20-40 s; the membrane is placed in the hot water bath again at the temperature of 80-100 ℃ for 5-8 min.
According to another aspect of the present invention, there is provided a conductive forward osmosis membrane obtained by the above-described preparation method.
According to another aspect of the present invention there is provided the use of an electrically conductive forward osmosis membrane as described above in water treatment.
The beneficial effects of the invention are as follows:
the conductive forward osmosis membrane prepared by the invention is characterized in that dopamine nano particles are deposited on the inner surface of a tubular coal-based carbon membrane through vacuum suction filtration, the inner surface of the carbon membrane which is rough, hydrophobic and has macropore defects is covered, and a hydrophilic middle layer with uniform pore size distribution is formed; and a complete continuous polyamide layer is obtained through interfacial polymerization, and the polyamide layer has good permeability and excellent selectivity; the finally prepared conductive forward osmosis membrane realizes good conductivity and chemical stability, and solves the problems of poor conductivity or unstable conductivity of the composite conductive forward osmosis membrane.
When the conductive forward osmosis membrane is used for treating polluted water in a mode that the polyamide layer faces to the drawing liquid, the membrane is used as an electrode under the condition of an external electric field, and the conductivity of the outer surface with large surface area can reduce the deposition of pollutants on the surface of the membrane through electrostatic repulsion and oxidization.
The conductive forward osmosis membrane is applied to the field of sewage treatment, and can relieve the pollution of the forward osmosis membrane by combining electrochemical action, so that the performance of the membrane is improved, and the conductive forward osmosis membrane has great theoretical significance and application value.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a conductive forward osmosis membrane according to the present invention;
FIG. 2 is a graph showing the effect of applied voltage on the flux and flux recovery of rhodamine B solution treated with the conductive forward osmosis membrane prepared in example 2;
wherein, (a) is a flux reduction curve of a rhodamine B solution treated by a conductive carbon-based forward osmosis membrane under different voltages;
wherein, (B) is the flux recovery rate and the retention rate of the rhodamine B solution treated by the conductive carbon-based forward osmosis membrane under different voltages;
FIG. 3 is a schematic diagram showing the effect of applied voltage on flux and flux recovery of the conductive forward osmosis membrane treated chrome black T solution prepared in example 2;
wherein, (a) is a flux reduction curve of a chromium black T solution treated by a conductive carbon-based forward osmosis membrane under different voltages;
wherein, (b) is the flux recovery rate and the rejection rate of the conductive carbon-based forward osmosis membrane treated chromium black T solution under different voltages.
Detailed Description
As shown in fig. 1, the invention provides a preparation method of a conductive forward osmosis membrane, which comprises the following steps:
(1) Preparing polydopamine nanoparticle dispersion liquid;
as a preferred preparation method: firstly, mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; oscillating the dopamine hydrochloride solution for 0.5-1.5 h to oxidize and self-polymerize the dopamine hydrochloride to obtain a polydopamine solution; and then performing ultrasonic dispersion on the polydopamine solution to obtain polydopamine nanoparticle dispersion liquid.
Wherein preferably, the amount of the dopamine hydrochloride powder is 0.1-0.2 g based on 100mL of water; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
(2) Preparing a polydopamine nanoparticle interlayer: taking a certain volume of polydopamine nanoparticle dispersion liquid, passing through a tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum suction filtration; the deposition amount of polydopamine nano particles on the inner surface of the tubular coal-based carbon membrane is preferably 0.4-1.3mg/cm 2 。
(3) A continuous polyamide layer was prepared on the surface of the polydopamine nanoparticle by interfacial polymerization.
As a preferred preparation method: vertically fixing the membrane obtained in the step (2), enabling 1-7% of m-phenylenediamine solution to pass through the inner surface of the membrane at a flow rate of 1-5 mL/min, soaking for 1-10 min, and removing superfluous solution on the surface; then enabling 0.1 to 0.3 mass percent of trimesic chloride solution to pass through the inner surface of the membrane to react for 1 to 5 minutes at the same flow rate; standing for 3-5 min, and placing the membrane in a hot water bath at 80-100 ℃ for crosslinking for 1-3 min; then taking out the membrane, soaking the membrane in sodium hypochlorite solution with the concentration of 0.1-0.5 g/L for 1-3 min, and then soaking the membrane in sodium bisulphite solution with the concentration of 1-3 g/L for 20-40 s; and then placing the membrane in a hot water bath at 80-100 ℃ for 5-8 min again to obtain the conductive forward osmosis membrane.
The conductive forward osmosis membrane prepared by the method can be used for water treatment, for example, as a filtering membrane in a water treatment device or equipment.
For a better understanding of the present invention, the following detailed description of the present invention will be made with reference to specific examples and corresponding comparative examples, but the specific examples described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The starting materials used in the examples and comparative examples of the present invention are commercially available or may be synthesized by methods known in the art.
Example 1:
an electrically conductive forward osmosis membrane was prepared as follows:
(1) Preparing a polydopamine nanoparticle dispersion liquid: 0.2g of dopamine hydrochloride is weighed and dissolved in 100mL of Tris solution with pH of 8.5 and concentration of 50mM to obtain dopamine hydrochloride solution; oscillating the dopamine hydrochloride solution for 1h to enable the dopamine hydrochloride to be oxidized and self-polymerized to obtain a polydopamine solution; and carrying out ultrasonic treatment on the polydopamine solution to obtain polydopamine nanoparticle dispersion liquid.
(2) Preparing a polydopamine nanoparticle interlayer: taking 5mL of the polydopamine nanoparticle dispersion liquid obtained in the step (1), passing through a peristaltic pump at a flow rate of 3mL/min in a tube of the tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane by vacuum filtration under the pressure of 0.2 Mpa. Finally, the deposition amount of the polydopamine nano-particles on the inner surface of the tubular coal-based carbon membrane is 0.4mg/cm 2 。
(3) Preparing a continuous polyamide layer on the surface of the polydopamine nanoparticle by interfacial polymerization: vertically fixing the membrane obtained in the step (2), enabling 3.0wt% of m-phenylenediamine solution to pass through the inner surface of the membrane at a flow rate of 3mL/min, soaking for 5min, and removing superfluous solution on the surface; then, allowing 0.15wt% of trimesic chloride solution to pass through the inner surface of the membrane at the same flow rate to react for 1.5min, standing for 3min, placing the membrane in a hot water bath at 90 ℃ to crosslink for 2min, taking out, and placing the membrane in sodium hypochlorite at 0.2g/L to soak for 2min; then soaking in 1g/L sodium bisulphite solution for 0.5min, and then placing the membrane in a hot water bath at 90 ℃ for 6min again to obtain the conductive forward osmosis membrane of the embodiment.
The water flux and the salt flux of the conductive forward osmosis membrane are respectively obtained by the formula (1) and the formula (2):
wherein DeltaV-volume change of the drawing liquid, L; a-effective membrane area, m 2 The method comprises the steps of carrying out a first treatment on the surface of the Δt-interval time, h.
Wherein V is t -the volume of draw solution at the end of the test, L; c (C) t -the salt concentration of the draw solution at the end of the test, mol/L; v (V) 0 -an initial volume of draw solution, L; c (C) 0 -initial salt concentration of the draw solution, mol/L.
The water flux of the conductive forward osmosis membrane obtained in example 1 was measured to be 7.5L/(m) 2 H) reverse salt flux of 10.2 g/(m) 2 ·h)。
Example 2
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 1, except that in step (2), the volume of polydopamine nanoparticle dispersion was 10mL, and the deposition amount of the final polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane was 0.91mg/cm 2 。
According to the measurement method of example 1, the measurement was performedThe water flux of the conductive forward osmosis membrane obtained in example 2 is 10.75L/(m) 2 H) the reverse salt flux was 1.83 g/(m) 2 ·h)。
Example 3
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 1, except that in step (2), the volume of polydopamine nanoparticle dispersion was 15mL, and the deposition amount of the final polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane was 1.23mg/cm 2 。
The water flux of the conductive forward osmosis membrane obtained in example 3 was 7.17L/(m) by the measurement method of example 1 2 H) reverse salt flux of 1.65 g/(m) 2 ·h)。
Example 4
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of the m-phenylenediamine solution was 1wt%.
The water flux of the conductive forward osmosis membrane obtained in example 4 was 15.01L/(m) according to the measurement method of example 1 2 H) reverse salt flux of 6.1 g/(m) 2 ·h)。
Example 5
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of the m-phenylenediamine solution was 5wt%.
The water flux of the conductive forward osmosis membrane obtained in example 5 was 10.37L/(m) by the measurement method of example 1 2 H) reverse salt flux of 6.43 g/(m) 2 ·h)。
Example 6
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of the m-phenylenediamine solution was 7wt%.
The water flux of the conductive forward osmosis membrane obtained in example 6 was 11.64L/(m) by the measurement method of example 1 2 H) the reverse salt flux was 106.97 g/(m) 2 ·h)。
Example 7
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of trimesoyl chloride solution was taken to be 0.1wt%.
The water flux of the conductive forward osmosis membrane obtained in example 7 was 16.21L/(m) by the measurement method of example 1 2 H) the reverse salt flux was 55.28 g/(m) 2 ·h)。
Example 8
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of trimesoyl chloride solution was taken to be 0.2wt%.
The water flux of the conductive forward osmosis membrane obtained in example 8 was 8.39L/(m) according to the measurement method of example 1 2 H) reverse salt flux of 1.78 g/(m) 2 ·h)。
Example 9
An electrically conductive forward osmosis membrane was prepared according to the procedure of example 2, except that in step (3), the concentration of trimesoyl chloride solution was taken to be 0.3wt%.
The water flux of the conductive forward osmosis membrane obtained in example 9 was 7.08L/(m) by the measurement method of example (1) 2 H) reverse salt flux 11.16 g/(m) 2 ·h)。
The treatment of the positively charged dye-mitigating membrane with the conductive forward osmosis membrane prepared in the above example was studied as follows:
an anti-fouling experiment was performed using the conductive forward osmosis membrane prepared in example 2 with rhodamine B solution at a concentration of 100ppm and a ph of 4 as a target contaminant. Figure 2 shows the effect of applied voltage on the flux and flux recovery of the conductive forward osmosis membrane. When a +1.5V voltage was applied to the membrane, the flux was increased by 21.57% after the end of 8 hours of operation compared to no voltage, and the flux recovery was increased by 4.5%.
The conductive forward osmosis membrane prepared in the above example was treated with negatively charged dye to alleviate membrane fouling as follows:
an anti-fouling experiment was performed using the conductive forward osmosis membrane prepared in example 2 with a concentration of 100ppm and a ph of 6 of chrome black T solution as a target contaminant. Figure 3 shows the effect of applied voltage on the flux and flux recovery of the conductive forward osmosis membrane. When a voltage of-1.5V was applied to the membrane, the flux was increased by 14.47% and the flux recovery was increased by 4.1% after the end of 8 hours of operation compared to the absence of the voltage.
Studies on the conductive forward osmosis membrane to treat positively and negatively charged dyes to relieve membrane pollution show that the anti-pollution performance of the conductive membrane depends on the surface charge of pollutants. Membrane contamination is reduced when the contaminants and the membrane surface have the same charge; membrane fouling is exacerbated when the contaminants and the membrane surface have opposite charges.
By preparing a carbon film substrate with a deposition amount of 0.4-1.3mg/cm 2 The conductive carbon-based forward osmosis membrane prepared by the polydopamine nanoparticle interlayer has good permeability. When the deposition amount of the polydopamine nano-particles is 0.91mg/cm 2 When the conductive carbon-based forward osmosis membrane is used, the carbon membrane substrate is completely covered to form a hydrophilic middle layer with uniform pore size distribution, and the prepared conductive carbon-based forward osmosis membrane has optimal permeability.
Based on the above, the influence of the concentration of the m-phenylenediamine solution and the concentration of the trimesic acid chloride solution on the forward osmosis performance of the prepared conductive carbon-based forward osmosis membrane is respectively explored. The concentration range of the m-phenylenediamine solution is 1-5 wt%, the concentration range of the trimesoyl chloride solution is 0.15-0.3 wt%, the prepared conductive carbon-based forward osmosis membrane has good forward osmosis performance, and when the concentration of the m-phenylenediamine solution is 3wt% and the concentration of the trimesoyl chloride solution is 0.15wt%, the performance of the prepared conductive carbon-based forward osmosis membrane is optimal. And too much m-phenylenediamine (at a concentration of 7 wt%) or trimesoyl chloride solution (at a concentration of 0.3 wt%) may deteriorate the forward osmosis performance of the polyamide layer by interrupting the formation of the polyamide network to cause defects in the polyamide layer.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (9)
1. The preparation method of the conductive forward osmosis membrane is characterized by taking a tubular coal-based carbon membrane as a supporting layer, depositing polydopamine nano particles on the inner surface of the tubular coal-based carbon membrane by a vacuum suction filtration method, and preparing a continuous polyamide layer on the surface of the polydopamine nano particles by interfacial polymerization to obtain the conductive forward osmosis membrane;
wherein the deposition amount of the polydopamine nano particles on the inner surface of the tubular coal-based carbon membrane is 0.4-1.3mg/cm 2 。
2. The method for preparing a conductive forward osmosis membrane according to claim 1, comprising the steps of:
(1) Preparing polydopamine nanoparticle dispersion liquid;
(2) Preparing a polydopamine nanoparticle interlayer: allowing the polydopamine nanoparticle dispersion liquid obtained in the step (1) to pass through the tubular coal-based carbon membrane, and depositing polydopamine nanoparticles on the inner surface of the tubular coal-based carbon membrane through vacuum suction filtration;
(3) And preparing a continuous polyamide layer on the surface of the polydopamine nanometer particle through interfacial polymerization.
3. The method for preparing a conductive forward osmosis membrane according to claim 2, wherein in the step (1), the method for preparing the polydopamine nanoparticle dispersion liquid comprises: mixing dopamine hydrochloride powder with a Tris solution to obtain a dopamine hydrochloride solution; oscillating the dopamine hydrochloride solution for 0.5-1.5 h to oxidize and self-polymerize the dopamine hydrochloride to obtain a polydopamine solution; and performing ultrasonic dispersion on the polydopamine solution to obtain the polydopamine nanoparticle dispersion liquid.
4. A method of producing an electrically conductive forward osmosis membrane according to claim 3, characterized in that the dopamine hydrochloride powder is 0.1-0.2 g based on 100mL water; the concentration of the Tris solution is 0.05-0.2 g/L, and the pH value is 8-9.
5. The method for preparing a conductive forward osmosis membrane according to claim 2, wherein in the step (3), the continuous polyamide layer is prepared on the surface of the polydopamine nanoparticle by interfacial polymerization, and the method comprises the following steps: vertically fixing the membrane obtained in the step (2), enabling 1-7% of m-phenylenediamine solution to pass through the inner surface of the membrane at a flow rate of 1-5 mL/min, soaking for 1-10 min, and removing superfluous solution on the surface; then enabling 0.1 to 0.3 mass percent of trimesic chloride solution to pass through the inner surface of the membrane to react for 1 to 5 minutes at the same flow rate; after standing for a certain time, placing the membrane in a hot water bath for crosslinking; then taking out the membrane and sequentially placing the membrane into sodium hypochlorite solution and sodium bisulphite solution for soaking; and then placing the membrane in a hot water bath again to obtain the conductive forward osmosis membrane.
6. The method for producing a conductive forward osmosis membrane according to claim 5, characterized in that the resting time is 3 to 5min; the temperature of the cross-linking in the hot water bath is 80-100 ℃ and the time is 1-3 min.
7. The method for preparing a conductive forward osmosis membrane according to claim 5, wherein the concentration of the sodium hypochlorite solution is 0.1-0.5 g/L, and the soaking time is 1-3 min; the concentration of the sodium bisulphite solution is 1-3 g/L, and the soaking time is 20-40 s; the membrane is placed in the hot water bath again at the temperature of 80-100 ℃ for 5-8 min.
8. An electrically conductive forward osmosis membrane, characterized in that it is obtained by the preparation method according to any one of claims 1 to 7.
9. Use of the electrically conductive forward osmosis membrane of claim 8 in water treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210539765.7A CN114931863B (en) | 2022-05-18 | 2022-05-18 | Conductive forward osmosis membrane and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210539765.7A CN114931863B (en) | 2022-05-18 | 2022-05-18 | Conductive forward osmosis membrane and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114931863A CN114931863A (en) | 2022-08-23 |
CN114931863B true CN114931863B (en) | 2024-01-26 |
Family
ID=82863882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210539765.7A Active CN114931863B (en) | 2022-05-18 | 2022-05-18 | Conductive forward osmosis membrane and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114931863B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102527257A (en) * | 2011-12-31 | 2012-07-04 | 大连理工大学 | Preparation method of conductive carbon membrane |
CN108654408A (en) * | 2018-05-16 | 2018-10-16 | 东华大学 | A kind of PDA is modified hot pressing nanofiber forward osmosis membrane and preparation method thereof |
CN111992039A (en) * | 2020-09-02 | 2020-11-27 | 天津工业大学 | Method for preparing high-performance nanofiltration membrane by constructing ZIF-8 intermediate layer |
US20210060497A1 (en) * | 2019-08-28 | 2021-03-04 | Tongji University | Thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and preparation method thereof |
CN112473372A (en) * | 2020-12-07 | 2021-03-12 | 江南大学 | Conductive forward osmosis membrane and preparation method thereof |
-
2022
- 2022-05-18 CN CN202210539765.7A patent/CN114931863B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102527257A (en) * | 2011-12-31 | 2012-07-04 | 大连理工大学 | Preparation method of conductive carbon membrane |
CN108654408A (en) * | 2018-05-16 | 2018-10-16 | 东华大学 | A kind of PDA is modified hot pressing nanofiber forward osmosis membrane and preparation method thereof |
US20210060497A1 (en) * | 2019-08-28 | 2021-03-04 | Tongji University | Thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and preparation method thereof |
CN111992039A (en) * | 2020-09-02 | 2020-11-27 | 天津工业大学 | Method for preparing high-performance nanofiltration membrane by constructing ZIF-8 intermediate layer |
CN112473372A (en) * | 2020-12-07 | 2021-03-12 | 江南大学 | Conductive forward osmosis membrane and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114931863A (en) | 2022-08-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108159888B (en) | Preparation method of super-hydrophilic ultrafiltration membrane with photocatalytic performance | |
CN109550406B (en) | Preparation method of amphoteric particle in-situ constructed metal organic framework separation membrane | |
Li et al. | PVDF grafted Gallic acid to enhance the hydrophilicity and antibacterial properties of PVDF composite membrane | |
CN112473372B (en) | Conductive forward osmosis membrane and preparation method thereof | |
CN110182906B (en) | Treatment process for degrading organic wastewater by conductive organic membrane coupling filtering system | |
Bandehali et al. | A new type of [PEI-glycidyl POSS] nanofiltration membrane with enhanced separation and antifouling performance | |
JP5837480B2 (en) | Composite semipermeable membrane | |
CN109603555B (en) | Preparation method of ultralow-pressure high-flux metal organic nanoparticle assembled nanofiltration membrane | |
US20150344339A1 (en) | Water treatment method | |
CN110841487B (en) | Preparation method of seawater desalination membrane | |
CN110960987B (en) | High-performance nano hybrid reverse osmosis membrane and preparation method thereof | |
WO2019153946A1 (en) | High-performance forward osmosis membrane, preparation method therefor and application thereof | |
CN112844046A (en) | Positively charged nanofiltration membrane and preparation method thereof | |
CN105148750A (en) | Method for modifying surface of polyamide composite film | |
CN105498546B (en) | A kind of reverse osmosis composite membrane of nanometer of conjugated polymer doping vario-property | |
CN114016285A (en) | Preparation method of functional nanofiber membrane for seawater desalination | |
Wu et al. | A novel conductive carbon-based forward osmosis membrane for dye wastewater treatment | |
CN114931863B (en) | Conductive forward osmosis membrane and preparation method and application thereof | |
CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
CN115069090B (en) | Intelligent nanofiltration membrane with double-electric-layer surface and preparation method thereof | |
CN114917755A (en) | Nano composite forward osmosis membrane with antibacterial effect and preparation method and application thereof | |
JP2013180263A (en) | Porous material | |
Wang et al. | The efficient treatment of pickling wastewater using a self-assembled in situ polymerized ceramic membrane with graphene/carbon nanotubes/polypyrrole | |
CN113926319A (en) | Composite membrane and preparation method and application thereof | |
CN111530296A (en) | Polyamide reverse osmosis membrane based on fluorine-containing dichlorosilane and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20240103 Address after: Room 1020, building 12, Shifoying Xili, Chaoyang District, Beijing 100025 Applicant after: Beijing baoshengtong International Electrical Engineering Technology Co.,Ltd. Address before: No. 399 Binshui West Road, Jingwu Town, Xiqing District, Tianjin 300380 Applicant before: TIANJIN POLYTECHNIC University |
|
TA01 | Transfer of patent application right | ||
GR01 | Patent grant | ||
GR01 | Patent grant |